CN1083592A - Organize determining of carbon equivalent in the modified cast iron - Google Patents

Organize determining of carbon equivalent in the modified cast iron Download PDF

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Publication number
CN1083592A
CN1083592A CN93105222A CN93105222A CN1083592A CN 1083592 A CN1083592 A CN 1083592A CN 93105222 A CN93105222 A CN 93105222A CN 93105222 A CN93105222 A CN 93105222A CN 1083592 A CN1083592 A CN 1083592A
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melt
temperature
cast iron
iron
carbon
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CN1033664C (en
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S·L·巴科鲁德
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SINTER CAST Ltd
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C1/00—Refining of pig-iron; Cast iron
    • C21C1/10—Making spheroidal graphite cast-iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D2/00—Arrangement of indicating or measuring devices, e.g. for temperature or viscosity of the fused mass
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N25/00—Investigating or analyzing materials by the use of thermal means
    • G01N25/02—Investigating or analyzing materials by the use of thermal means by investigating changes of state or changes of phase; by investigating sintering
    • G01N25/04—Investigating or analyzing materials by the use of thermal means by investigating changes of state or changes of phase; by investigating sintering of melting point; of freezing point; of softening point
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/20—Metals
    • G01N33/202—Constituents thereof
    • G01N33/2022—Non-metallic constituents
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/20—Metals
    • G01N33/205—Metals in liquid state, e.g. molten metals

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  • Engineering & Computer Science (AREA)
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  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Food Science & Technology (AREA)
  • Medicinal Chemistry (AREA)
  • Investigating And Analyzing Materials By Characteristic Methods (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
  • Investigating Or Analyzing Materials Using Thermal Means (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)
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Abstract

The present invention relates to a kind of method of determining to organize modified cast iron melt carbon equivalent, and utilize this method adjustment to organize the composition of modified cast iron melt.This method is to be based upon iron block with one or more low carbon contents to be incorporated on the basis in the sample receiver.The size that iron block has should make its alkanisation fully not when container is full of melt.Along with solidifying of melt noted melt temperature (Fig. 2).Use this method, when temperature is passed through γ phase liquidus curve, can obtain a completely specified temperature, perhaps obtain the temperature difference of organizing the modified cast iron eutectic temperature with respect to quite similar type.Determine its carbon equivalent according to the phasor that is suitable for this curved matter cast iron.Adjust its CE value by the iron that adds carbon and/or silicon or low carbon content.

Description

Organize determining of carbon equivalent in the modified cast iron
The carbon equivalent of organizing modified cast iron that the present invention relates to spheroidal-graphite cast iron, vermicular cast iron one class is determined method.
The binary phase diagraml of iron and carbon only has limited meaning in casting industry, always contain alloying element because be used to produce all material of cast iron, and as silicon, manganese and impurity such as sulphur, phosphorus etc., these elements can change facies relationship.Some element wherein can replace carbon with different ratios, thereby influences phasor.As the result of various elements to the total effect of phasor, when determining the liquidus temperature that concrete composition determined of melt, involved carbon equivalent is that CE can be expressed as:
CE＝%C+%Si/x+%P/Y+…
X in the formula is 3-4, and Y is 3-6, and in the U.S., this formula is reduced to usually:
CE＝%C+%Si/3。
This formula operating position is as described below.
Why the formula of this simplification can use, and is because phosphorus content is very low in the molten cast iron that uses in the foundary industry, thereby can ignores.When making vermicular cast iron and spheroidal-graphite cast iron, interested CE scope is 3-5.
The disclosed iron-carbon of great majority-silicon phasor relates to the curing condition of grey cast iron (graphite crystal growth wherein just be extension with the undressed cast iron branch sheet).In this system, between γ iron (austenite) and the graphite flake CE be about 4.35% and temperature eutectic reaction takes place when being 1155 ℃.The cast iron of carbon content or CE＜4.35% is commonly referred to hypoeutectic cast iron, carbon content or CE＞4.35% then be called hypereutectic cast iron.As mentioned above, this definition is only just meaningful to the grey cast iron with flaky graphite.
Utilize phase transition temperature can determine the actual CE value of hypoeutectic cast iron.Temperature at sample begins to separate out the γ phase time by liquidus curve, and cooling curve can demonstrate temperature and stagnate.The reason that the temperature stagnation occurs is that the growth kinetics (characteristic) of austenite phase is very high, in addition because same conclusion also is applicable to the heat of crystallization of γ phase.
Form a point tangible and that quite determine on the temperature-time curve that these factors help to have temperature to stagnate within a certain period of time.
This principle is applied to casting industry for a long time.For example, previous disclosed SE-B-350124 proposes a kind of device that is used to set up the cooling curve of this smelting iron liquid.
But, the not success of effort of adopting the CE that uses the same method to determine hypereutectic alloy.Laminar carbon is first solid phase that this melt is separated out.This carbon crystal is not forming core immediately after by liquidus curve, and the latent heat that it produced seldom and scatters in a temperature range.Therefore, variation on the freezing curve being got in touch with the clear and definite phase transition temperature that can determine CE is impossible.
This problem is to be solved by the method that SE-B-342508 points out.The document points out, can be when adding some element and in melt, is inhibited in the formation of graphite, and it is cold that melt will keep, in reaching the metastable state system till the corresponding line of γ iron and cementite.First that solidifies formation in highly hypereutectic melt is cementite mutually, because its high growth kinetics characteristic, this cementite will discharge enough heat, makes within a certain period of time temperature reduce and stagnates.It seems that the applicant of above-mentioned patent SE-B-342508 do not consider such fact: two kinds of diverse melts-a kind of are to have Hypoeutetic Alloy that nascent γ precipitates mutually and another kind is a hypereutectic with nascent cementite precipitation-will provide same result.This application people has also ignored the zone of the very important γ-liquidus curve displacement between stable state and metastable state.
The applicant of above-mentioned patent thinks that also some element can suppress the formation of graphite, and tellurium, boron and cerium be effective elements the most seemingly, although also mentioned magnesium in the document.Though such statement has correct part, utilize limited interpolation cerium (and other rare earth element and magnesium) to produce millions of tons of spheroidal-graphite cast iron every year, and the danger that generates cementite is very small.
To studies show that of modified cast iron (promptly added rare earth metal and/or magnesium after), such cast iron must illustrate with diverse phasor, in the described phasor, liquidus curve, CE and the eutectic reaction temperature of γ-liquidus curve, rotten graphite nodule taken place to move.
The present invention is described in detail with reference to the accompanying drawings.
Fig. 1 shows the zone around the eutectic reaction in a phasor that relates to modified cast iron.
Fig. 2 shows freezing curve of drawing according to known method and the freezing curve of drawing according to the inventive method.
It is that the forming core level is 100 ± 50 graphite nodules/[millimeter] the coupon of 2.5cm to diameter that Fig. 1 shows from general iron-carbon-silicon phasor 2The situation of change of spheroidal-graphite cast iron phasor.The CE of this eutectic composition is approximately 4.7%, its eutectic freezing temperature is about 1140 ℃, at this point place, γ iron and graphite nodule are separated out according to lever law, under the lower situation of CE value, γ is mutually basically with the development of dendrite form, and CE＞about 4.7% o'clock, graphite nodule just can be separated out from melt, and these graphite nodules tend to rise to the top (floating) of melt.Why select this 100 ± 50 graphite nodules/mm 2Rotten level be because in most of the cases, this level has been represented the virtual condition at based process (just add FeSiMg and FeSi and randomly dose the rare earth metal of specified rate) back spheroidal-graphite cast iron.
When in melt, reaching above-mentioned level, just can highly precisely be defined as obtaining the alterant quantity of the required interpolation of desired graphite nodule quantity levels (being the number of graphite ball of every simple grain area).Content of magnesium residual in such cast iron must be higher than 0.02%(weight).
With regard to casting industry, what wish most is the composition that the composition that foundry goods had produced just is lower than the eutectic point that dynamically moves.In this composition range, for example, the CE value is separated out the netted thing of tiny dendroid in the whole cast iron (product) when solidifying beginning between 4.55-4.65.This net provides stability to a certain degree to cast iron, and stops the graphite nodule that forms in the next stage of this process to float in melt.The netted shape thing of this tiny dendriform is not seriously placed restrictions on melt and is flowed in the interdendritic, thereby has reduced the danger that forms loose and shrinkage cavity.
In technological process, the method that can be reliably the CE value of reality be controlled in such narrow range has very big meaning for foundry industry.Known method can't produce desirable result in the past, its reason or lack precision, or since have cover necessary situation, undesirable carbonide forms and it can not be applied to organize modified cast iron.
According to the present invention, have now found that, be used for heat and analyze and obtain sample about the crystal property information of organizing rotten melt, as the sort of sample that describes in detail in the above-mentioned US-A-4667725 patent, after carrying out some other measurement, can also be used to determine be in the actual CE value of the spheroidal-graphite cast iron and the vermicular cast iron of molten condition, their CE value is the highest can to reach actual eutectic point, that is to say that accessible in these cases CE value is 4.7%.
The method of US-A-4667725 is based on, from relevant molten cast iron, take out sample, put into a container that immerses this melt and be preheated or heat, this container disposes two temperature sensors (for example thermopair), one of them is arranged on the position near container inner wall, and another is arranged in the container and the nearest equidistant central part of outer wall.
When using such sample receiver, generally can observe owing to what more or less show significantly and reduce the growth of the γ dendrite that causes in sample center setting rate.This method is similar with the method for the known accurate CE value that is used for determining relevant material.But have now found that, these methods, for example the method described in the SE-B-342508 can not solve those problems as basis of the present invention.
According to the present invention, have now found that this problem can be solved mutually by triggering forming core with a kind of mechanism and beginning to separate out γ, described mechanism can obtain accurate thermal signal with guaranteeing continuously when specimen temperature is crossed the liquidus curve of relevant phasor.
This mechanism can constitute by one or more pure iron pieces being provided and making it to contact with melt in the sample receiver.Employed pure iron piece should only contain iron in a small amount, thereby make it as a whole sample mean composition is not had tangible influence, but, its contained iron amount should be enough to make it container filled with sample and then carry out the sample cooling time can not melt fully and with the sample melt mixed.In fact, the pure iron that this means an a small amount of is present in the sample.In cooling procedure, this a spot of iron will crystallization under the beguine temperature much higher according to the γ phase liquidus temperature of the average composition calculating of sample.Therefore, when the γ phase liquidus curve of temperature by the system of the main composition partly of employed representative sample, formed the crystallization of a spot of γ phase.
The cooling of sample inside must be later than the cooling velocity at chamber wall place, and, iron block must be placed in the body volume (bulk volume) of melt, with the instantaneous surface reaction of avoiding usually occurring in the chamber wall place and extending to 2-3 millimeter in the body volume.
Another kind of way is, the heat insulation of the limited part by wall can make the heat transmission of passing chamber wall reduce, and heat insulation can be produced by the mild carbon steel on the insulating point that directly is attached to chamber wall or an iron separately.
Just in this, γ phase dendrite can begin growth immediately, expands in the whole volume of sample.The beginning to produce and to characterize by the obvious bending on the freezing curve of obtaining at the sample center of this γ phase dendrite, in the distortion of temperature-time curve, can clearly be seen that this bending, can think that this is owing to γ effect (γ-function) cause.This temperature, as a definite temperature (℃) relevant with actual liquidus temperature, perhaps can be with respect to the chemical analysis of many samples and by verification.More meaningfully, the steady temperature of γ being grown mutually when following eutectic reaction after the dendritic growth in starting point and the process of setting closely is linked to each other.Fig. 2 has showed the present invention, and has provided the freezing curve that is obtained by the temperature sensor that is positioned at the center, wherein, and the situation of the γ dendritic growth when a) expression does not have to use the triggering agent that is made of pure iron.Can see that by Fig. 2 in a certain moment in the zone of hatching, promptly near T γ, dendritic growth begins.When using the triggering agent, it is a definite temperature that T γ can be picked out.Particularly advantageously be, the difference between T γ and the Tc maximal value can be utilized, and this difference is marked in the drawings and made △ T.So just make from dendritic growth and begin directly to obtain to the relation of the temperature and time of eutectic reaction.When modified cast iron was organized in casting, this just provided a kind of better image of process of setting progress to describe, and this method also makes can establish the CE value with pinpoint accuracy.
Like this, if obtaining to utilize T γ or △ T(T after the data from solidifying sample cMax is determined) actual value just can determine the actual temp of T γ, and also can determine the CE value of this melt by iron-carbon-silicon figure with movement value relevant with the alloy addition in the relevant melt.Fig. 2 has showed a figure b), figure b) to relate to diameter be to have 100 ± 50 graphite nodules/[mm] in 2.5 centimetres the coupon 2Spheroidal-graphite cast iron.If temperature T γ is 1150 ℃ or △ T=10k, under this particular case, just can calculate CE by means of Fig. 1, its value is 4.52%.
The final adjustment of rotten performance reaches by further interpolation ferrosilicon (Fe+75%Si).But the interpolation of this ferrosilicon can cause the increase of the final CE value of founding materials, and this is must take in when calculating the carbon equivalent of founding materials.
For example, if add 0.16%Fe-75%Si again after having determined CE, the CE value will increase 0.04% so, can be easy to see this point from following formula:
(75%0.16)/and 100=0.12%Si, obtain thus: (0.12%Si)/3=0.04% CE
Therefore, the present invention is a kind of substantial improvement to method described in the US-A-4667725.The present invention proposes the program of similar sample procedure and the control intrinsic crystallographic property of molten cast iron such as metamorphic grade (degree of modifi cation) and nucleus number etc., in the past, it is impossible wanting to obtain carbon equivalent simultaneously in the mode that can reproduce, thereby and wants to obtain at short notice that pass through or popular numerical value can to adjust carbon equivalent before melt casting just more impossible.

Claims (2)

1, a kind of method of determining to organize modified cast iron melt carbon equivalent, wherein, the sample of getting described melt is put into one and is in the sampling receptacle of thermal equilibrium state with this melt, this sampling receptacle disposes a temperature sensor that is positioned at its center, allow sample solidify, and note time dependent temperature, it is characterized in that, the low iron block of the one or more carbon content of configuration in sample receiver, and make it to contact with fusant, the size of iron block should make it can not melt fully in process of setting, nor can make the average composition of melt that big variation takes place, and the cooling of iron block is later than the cooling at sample receiver wall place; Temperature by γ phase liquidus curve goes on record as a definite temperature, perhaps measuring with respect to the eutectic temperature of organizing modified cast iron of quite similar type and the temperature difference of proof test value goes on record, according to being applicable to that this phasor of modified cast iron of organizing determines carbon equivalent.
2, the application of the described method of claim 1 is characterized in that, determines the carbon equivalent of melt, in case of necessity, comes carbon equivalent is adjusted by the iron that adds carbon and/or silicon or low carbon content in melt.
CN93105222A 1992-04-09 1993-04-08 The determination of the carbon equivalent in structure modified cast iron Expired - Fee Related CN1033664C (en)

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SE9201141A SE470091B (en) 1992-04-09 1992-04-09 Method for determining the carbon equivalent of structure-modified cast iron melts
SE9201141-0 1992-04-09

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103388100A (en) * 2013-07-17 2013-11-13 天润曲轴股份有限公司 Method for controlling carbon equivalent of base iron and application of method
CN110253005A (en) * 2019-06-06 2019-09-20 郑石竹 A kind of preparation method and system of the optimization casting shrinkage cavity of control iron liquid eutectic degree
CN113088802A (en) * 2021-04-02 2021-07-09 广西玉柴机器股份有限公司 Production method of vermicular cast iron with low shrinkage tendency and vermicular cast iron

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* Cited by examiner, † Cited by third party
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SE502227C2 (en) * 1993-12-30 1995-09-18 Sintercast Ab Process for the continuous provision of pretreated molten iron for casting compact graphite iron articles
FR2731797B1 (en) * 1995-03-17 1997-04-11 Renault METHOD AND DEVICE FOR DETERMINING THE PRECIPITATION STRUCTURE OF THE GRAPHITE CONTAINED IN A CAST BEFORE CASTING
KR100749027B1 (en) 2006-06-23 2007-08-13 주식회사 포스코 Continuous casting machine and method using molten mold flux
KR100749026B1 (en) * 2006-06-23 2007-08-13 주식회사 포스코 Continuous casting machine using molten mold flux
EP3339848B1 (en) * 2016-12-23 2020-12-02 Fundación Azterlan Method to determine the carbon equivalent content of a cast iron alloy having a hypereutectic composition and equipment to carry it out

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Publication number Priority date Publication date Assignee Title
GB1038483A (en) * 1962-11-20 1966-08-10 Leeds & Northrup Co An expendable thermal phase change detector device
SE444817B (en) * 1984-09-12 1986-05-12 Sintercast Ab PROCEDURE FOR THE PREPARATION OF CASTING IRON
SE446775B (en) * 1985-02-05 1986-10-06 Stig Lennart Baeckerud DEVICE FOR THERMAL ANALYSIS AND MODIFICATION OF METAL MELTOR
SE466059B (en) * 1990-02-26 1991-12-09 Sintercast Ltd PROCEDURES FOR CONTROL AND ADJUSTMENT OF PRIMARY NUCLEAR FORM
SE469712B (en) * 1990-10-15 1993-08-30 Sintercast Ltd PROCEDURES FOR PREPARING THE IRON WITH COMPACT GRAPHITE
US5305815A (en) * 1992-10-30 1994-04-26 Queen's University Method and apparatus for predicting microstructure of cast iron

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103388100A (en) * 2013-07-17 2013-11-13 天润曲轴股份有限公司 Method for controlling carbon equivalent of base iron and application of method
CN110253005A (en) * 2019-06-06 2019-09-20 郑石竹 A kind of preparation method and system of the optimization casting shrinkage cavity of control iron liquid eutectic degree
CN110253005B (en) * 2019-06-06 2021-07-30 漳州海力机械制造有限公司 Preparation method and system for controlling molten iron eutectic degree to optimize casting shrinkage cavity
CN113088802A (en) * 2021-04-02 2021-07-09 广西玉柴机器股份有限公司 Production method of vermicular cast iron with low shrinkage tendency and vermicular cast iron

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EP0633817B1 (en) 1997-06-11
AU3964493A (en) 1993-11-18
ATE154267T1 (en) 1997-06-15
TW247939B (en) 1995-05-21
KR950700797A (en) 1995-02-20
EP0633817A1 (en) 1995-01-18
CA2133333A1 (en) 1993-10-28
BR9306195A (en) 1998-06-23
JP2584590B2 (en) 1997-02-26
FI944723A0 (en) 1994-10-07
WO1993020965A1 (en) 1993-10-28
ES2105250T3 (en) 1997-10-16
FI944723A (en) 1994-10-07
KR100263511B1 (en) 2000-09-01
RU94045912A (en) 1996-12-10
CN1033664C (en) 1996-12-25
SE9201141L (en) 1993-10-10
AU666371B2 (en) 1996-02-08
SE9201141D0 (en) 1992-04-09
DE69311542T2 (en) 1997-10-02
HUT69220A (en) 1995-08-28
SE470091B (en) 1993-11-08
DE69311542D1 (en) 1997-07-17
JPH07502819A (en) 1995-03-23
CZ244794A3 (en) 1995-05-17
US5577545A (en) 1996-11-26

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